Preparation and Thermal Decomposition of N,N'-Diacyl-N,N'-Dialkoxyhydrazines: Synthetic Applications and Mechanistic Insights

Almeida, Mauro Vieira de; Barton, Derek H. R.; Bytheway, Ian; Ferreira, J. A.; Hall, Michael B.; Liu, Wansheng; Taylor, Dennis K.; Thomson, Lisa

doi:10.1021/ja00122a018

Cited by 61 publications

(46 citation statements)

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“…In our study, N-benzoyl-N-benzyloxy-N ′-butoxy-N ′-(p-chlorobenzoyl)hydrazine (12a) decomposed at room temperature in CDCl 3 affording largely benzyl benzoate (13a) and butyl pchlorobenzoate (13b) from two, three-centre processes (Scheme 4, path B). Similarly, Barton and co-workers exclusively rearranged 12b to a 1:1 mixture of 13c and 13d (40 (2) for the methylated models 12e and 12f. They also reported that a concerted pathway to two molecules of ester and nitrogen was not viable.…”

Section: Rearrangement Of the Intermediate N-alkoxy-n-(n-methyl-mentioning

confidence: 99%

“…A related class of analogues, the N,N ′-diacyl-N,N ′-dialkoxyhydrazines 12, are readily generated by oxidative dimerization of hydroxamic esters (37)(38)(39)(40) and by dimerization of alkoxyamidyl radicals formed upon oxidation of hydroxamic esters or photolysis of N-alkoxy-N-haloamides (41,42). In a recent study we have demonstrated that these hydrazines exhibit all the hallmarks of anomeric amides (15).…”

Section: Rearrangement Of the Intermediate N-alkoxy-n-(n-methyl-mentioning

confidence: 99%

“…The discovery of the HERON reaction process instigated a reevaluation of the mechanistic details of this reaction by our group (44) and, coincidentally, by Barton and coworkers (40). Both studies involved the synthesis and thermal decomposition of an asymmetrical hydrazine.…”

Section: Rearrangement Of the Intermediate N-alkoxy-n-(n-methyl-mentioning

confidence: 99%

“…This concerted reaction was flagged by Barton and coworkers (40) as an excellent synthesis of sterically hindered esters. For example, decomposition of 12c afforded tertbutyl 1-adamantanecarboxylate (13e) in 87% yield.…”

Section: Rearrangement Of the Intermediate N-alkoxy-n-(n-methyl-mentioning

confidence: 99%

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The HERON reaction Origin, theoretical background, and prevalence

Glover¹,

Rauk²,

Buccigross³

et al. 2005

Can. J. Chem.

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Abstract:The origin of the HERON reaction is reviewed from a historical perspective and shown to have its foundation in the unusual properties of bisheteroatom-substituted amides, so-called anomeric amides. The reaction involves migration of anomerically destabilized oxo-substituents on an amide nitrogen to the amide carbon and dissociation of the amide bond. Computational work providing a theoretical basis for the reaction is presented, together with physical organic measurements that support results therefrom. The rearrangement has been observed in a number of chemical transformations of N-alkoxy-N-aminoamides, reactions of 1-acyloxy-1-alkoxydiazenes, N-alkoxy-N-aminocarbamates, Nalkoxyhydroxamic acids, as well as in the gas-phase reactions of N-acyloxy-N-alkoxyamides.Key words: HERON reaction, anomeric amides, rearrangements, hindered esters, concerted reactions. Résumé :On a fait une revue historique de l'origine de la réaction HERON et on montre que sa base réside dans les propriétés inhabituelles des amides portant des substituants bishétéroatomiques, les amides dits anomères. La réaction implique la migration de substituants oxo anomériquement déstabilisée de l'azote d'un amide vers le carbone de l'amide accompagnée d'une dissociation de la liaison amide. On présente un ensemble de calculs théoriques qui sert de base pour expliquer la réaction ainsi que des mesures de chimie organique physique qui supportent les résultats de ces calculs. Le réarrangement a été observé dans un certain nombre de transformations chimiques de N-alkoxy-N-aminoamides, dans les réactions de 1-acyloxy-1-alkyoxydiazènes, de N-alkoxy-N-aminocarbamates et d'acides N-alkoxyhydroxamiques ainsi que dans les réactions en phase gazeuse de N-acyloxy-N-alkoxyamides.

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Section: Rearrangement Of the Intermediate N-alkoxy-n-(n-methyl-mentioning

confidence: 99%

Section: Rearrangement Of the Intermediate N-alkoxy-n-(n-methyl-mentioning

confidence: 99%

Section: Rearrangement Of the Intermediate N-alkoxy-n-(n-methyl-mentioning

confidence: 99%

Section: Rearrangement Of the Intermediate N-alkoxy-n-(n-methyl-mentioning

confidence: 99%

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The HERON reaction Origin, theoretical background, and prevalence

Glover¹,

Rauk²,

Buccigross³

et al. 2005

Can. J. Chem.

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“…N2 elimination from hydrazine derivatives is not common, but such a reaction takes place in the case of the thermal decomposition of N,N'-diacyl-N,N'-dalkoxyhydrazines 153, which leads to formation of the corresponding esters and N 2 [136,137]. The reaction is stepwise, by elimination of e.g.…”

Section: Hydrazidesmentioning

confidence: 99%

Pyrolysis of hydrazine derivatives and related compounds with N N single bonds

Gaber

Wentrup

2017

Journal of Analytical and Applied Pyrolysis

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N‐Heteroatom‐Substituted Hydroxamic Esters

Glover

2010

Patai's Chemistry of Functional Groups

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Introduction Unusual Characteristics of N ‐Heteroatom‐Substituted Hydroxamic Esters N ‐Alkoxy‐ N ‐Haloamides N ‐Acyloxy‐ N ‐Alkoxyamides N , N ‐Dialkoxyamides N ‐Alkoxy‐ N ‐Aminoamides N ‐Alkoxy‐ N ‐Thioalkylamides Acknowledgement

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Preparation and Thermal Decomposition of N,N'-Diacyl-N,N'-Dialkoxyhydrazines: Synthetic Applications and Mechanistic Insights

Cited by 61 publications

References 0 publications

The HERON reaction Origin, theoretical background, and prevalence

The HERON reaction Origin, theoretical background, and prevalence

Pyrolysis of hydrazine derivatives and related compounds with N N single bonds

N‐Heteroatom‐Substituted Hydroxamic Esters

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Preparation and Thermal Decomposition of N,N'-Diacyl-N,N'-Dialkoxyhydrazines: Synthetic Applications and Mechanistic Insights

Cited by 61 publications

References 0 publications

The HERON reaction  Origin, theoretical background, and prevalence

The HERON reaction  Origin, theoretical background, and prevalence

Pyrolysis of hydrazine derivatives and related compounds with N N single bonds

N‐Heteroatom‐Substituted Hydroxamic Esters

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Product

Resources

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The HERON reaction Origin, theoretical background, and prevalence

The HERON reaction Origin, theoretical background, and prevalence